鲤鱼耳石Micro-CT特征与水域中重金属元素响应关系研究
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摘要
鱼耳石因为具有生物惰性而成为环境信息的良好载体,可以客观记录水体环境的历史变迁及低浓度污染物的富集。目前,国内外开展利用鱼耳石进行湖泊的水质评价及动态监测研究主要基于对水体及耳石进行微化学分析,另外,寻找各类简洁灵敏的标型特征证实鱼耳石与水体水质存在一定的耦合关系也非常必要。
本文将水质环境差异较大的白洋淀和密云水库两个研究区的鲤鱼耳石作为研究对象,首次将X射线断层扫描技术(CT)及Micro-CT技术运用到鲤鱼耳石对水环境中重金属元素的响应关系研究中,同时利用XRD、SEM、LA-ICP-MS等技术对鲤鱼耳石进行了物相、结构、形貌及富集元素的研究,扫描电镜下作者清楚地观察到了矢耳石日轮以及年轮界线;微区XRD实验显示两地鲤鱼耳石矿物种和晶体结构未见整体性差异,但晶胞参数略有差异,白洋淀水域晶胞参数出现明显畸变倾向,微耳石的晶胞参数a普遍比标准晶胞参数a小,矢耳石的晶胞参数a也普遍比标准晶胞参数a小,而晶胞参数b、c普遍比标准晶胞参数大,密云水库耳石晶胞参数在标准晶胞参数附近波动,无明显规律;LA-ICP-MS分析结果显示白洋淀水域耳石中的Cu和Pb含量大于密云水库相应元素的含量,密云水库耳石中的常量元素Mg含量高于白洋淀水域耳石中Mg的含量; Micro-CT实验数据统计表明白洋淀水域鲤鱼耳石的Micro-CT值高于密云水库鲤鱼耳石的Micro-CT值。
对以上实验结果与数据综合分析表明:研究区水质状况基本不会影响耳石中碳酸钙晶型的选择,但对晶胞参数略有影响,常量元素Mg、Ba及重金属元素Cu和Pb等共同导致了碳酸钙晶胞参数畸变。重金属元素Cu和Pb的富集程度是导致两研究区水域Micro-CT值差异的主要原因。原子序数大的Cu和Pb元素在白洋淀水域鲤鱼耳石中含量较高,直接导致了高密度体素的产生,当X射线入射过程中与Cu和Pb元素碰撞,由于Cu和Pb的原子系数大,其电子结合能高,密度高,原子结构最紧密,X射线可以被大量吸收,即对X射线的吸收系数大,进而导致Micro-CT值高。
综上,利用Micro-CT实验数据统计对比可以反映出鲤鱼耳石中原子序数大的重金属元素信息。耳石中的元素与水体元素具有相似的分布趋势,且对水体中相应元素有明显的富集作用。因此,鲤鱼耳石Micro-CT特征与水环境中重金属元素存在一定的耦合关系,可作为标型特征指示水体中重金属元素信息。
Otolith becomes a good environmental information carrier because of the biological inertia, and can objectively record the historical changes in the water environment and the enrichment of low concentrations of pollutants. At present, the research which otolith is used for the water quality evaluation and dynamic monitoring of lakes is mainly based on the micro-chemical analysis of the water body and otolith at home and abroad. It is necessary to find out some simple and sensitive typomorphic characters which can confirm there are some coupling relationship between otolith and the water quality.
This paper studies carp otolith from the Baiyangdian and the Miyun Reservoir whose water quality are different. X-ray tomography (CT) and Micro-CT technology are first applied to the study of the response relationship between carp otolith and the heavy metals in the water, while XRD, SEM, LA-ICP-MS techniques have been used to the study of otolith phase, structure, morphology and elemental enrichment. The author clearly observe daily growth rings and the growth ring boundary of sagittae under SEM; Micro-area XRD showed there is no overall difference in mineral species and crystal structure of otolith from the different waters, but there is a slightly different about lattice parameters, lattice parameters a of the lapillus is smaller than the standard lattice parameters in the Baiyangdian, while lattice parameters c of the sagittae is bigger than the standard lattice parameters; LA-ICP-MS analysis revealed that the contents of Cu and Pb of otoliths in Baiyangdian are higher than the contents of corresponding elements of otoliths in Miyun reservoir, the content of Mg of otoliths in Miyun reservoir is higher than the content of otoliths in the Baiyangdian; Micro-CT experimental data shows that the Micro-CT value of otolith from the Baiyangdian is higher than that r from the Miyun Reservoir.
Comprehensive analysis shows that: the water quality will not affect polymorph of calcium carbonate in otolith basically, but a slight impact on lattice parameters, Mg and the heavy metals Cu and Pb led to aberration of lattice parameters of calcium carbonate. The contents of Cu and Pb is the main factor to the the difference of Micro-CT value of otolith from different waters. The contents of Cu and Pb which have a high atomic number are higher in otolith from the Baiyangdian waters, resulting of the high density voxels. Cu and Pb have the characters: high atomic number, high electronic binding energy ,high density and the atomic structure is tightness .The X-ray collides with Cu and Pb and can be absorbed largely when the X-ray irradiate the otolith, which led to large absorption coefficient and the high value of Micro-CT. To sum up, information on heavy metals with high atomic number in the carp otolith can be reflected by statistical comparison of Micro-CT data. Elements in otoliths have the similar distribution trend with elements of the waters and can be obviously enriched. Therefore, there is the coupling relationship between Micro-CT character of carp otolith and the heavy metals in waters, which can be used to direct the information of the heavy metals in waters as typomorphic character.
本文将水质环境差异较大的白洋淀和密云水库两个研究区的鲤鱼耳石作为研究对象,首次将X射线断层扫描技术(CT)及Micro-CT技术运用到鲤鱼耳石对水环境中重金属元素的响应关系研究中,同时利用XRD、SEM、LA-ICP-MS等技术对鲤鱼耳石进行了物相、结构、形貌及富集元素的研究,扫描电镜下作者清楚地观察到了矢耳石日轮以及年轮界线;微区XRD实验显示两地鲤鱼耳石矿物种和晶体结构未见整体性差异,但晶胞参数略有差异,白洋淀水域晶胞参数出现明显畸变倾向,微耳石的晶胞参数a普遍比标准晶胞参数a小,矢耳石的晶胞参数a也普遍比标准晶胞参数a小,而晶胞参数b、c普遍比标准晶胞参数大,密云水库耳石晶胞参数在标准晶胞参数附近波动,无明显规律;LA-ICP-MS分析结果显示白洋淀水域耳石中的Cu和Pb含量大于密云水库相应元素的含量,密云水库耳石中的常量元素Mg含量高于白洋淀水域耳石中Mg的含量; Micro-CT实验数据统计表明白洋淀水域鲤鱼耳石的Micro-CT值高于密云水库鲤鱼耳石的Micro-CT值。
对以上实验结果与数据综合分析表明:研究区水质状况基本不会影响耳石中碳酸钙晶型的选择,但对晶胞参数略有影响,常量元素Mg、Ba及重金属元素Cu和Pb等共同导致了碳酸钙晶胞参数畸变。重金属元素Cu和Pb的富集程度是导致两研究区水域Micro-CT值差异的主要原因。原子序数大的Cu和Pb元素在白洋淀水域鲤鱼耳石中含量较高,直接导致了高密度体素的产生,当X射线入射过程中与Cu和Pb元素碰撞,由于Cu和Pb的原子系数大,其电子结合能高,密度高,原子结构最紧密,X射线可以被大量吸收,即对X射线的吸收系数大,进而导致Micro-CT值高。
综上,利用Micro-CT实验数据统计对比可以反映出鲤鱼耳石中原子序数大的重金属元素信息。耳石中的元素与水体元素具有相似的分布趋势,且对水体中相应元素有明显的富集作用。因此,鲤鱼耳石Micro-CT特征与水环境中重金属元素存在一定的耦合关系,可作为标型特征指示水体中重金属元素信息。
Otolith becomes a good environmental information carrier because of the biological inertia, and can objectively record the historical changes in the water environment and the enrichment of low concentrations of pollutants. At present, the research which otolith is used for the water quality evaluation and dynamic monitoring of lakes is mainly based on the micro-chemical analysis of the water body and otolith at home and abroad. It is necessary to find out some simple and sensitive typomorphic characters which can confirm there are some coupling relationship between otolith and the water quality.
This paper studies carp otolith from the Baiyangdian and the Miyun Reservoir whose water quality are different. X-ray tomography (CT) and Micro-CT technology are first applied to the study of the response relationship between carp otolith and the heavy metals in the water, while XRD, SEM, LA-ICP-MS techniques have been used to the study of otolith phase, structure, morphology and elemental enrichment. The author clearly observe daily growth rings and the growth ring boundary of sagittae under SEM; Micro-area XRD showed there is no overall difference in mineral species and crystal structure of otolith from the different waters, but there is a slightly different about lattice parameters, lattice parameters a of the lapillus is smaller than the standard lattice parameters in the Baiyangdian, while lattice parameters c of the sagittae is bigger than the standard lattice parameters; LA-ICP-MS analysis revealed that the contents of Cu and Pb of otoliths in Baiyangdian are higher than the contents of corresponding elements of otoliths in Miyun reservoir, the content of Mg of otoliths in Miyun reservoir is higher than the content of otoliths in the Baiyangdian; Micro-CT experimental data shows that the Micro-CT value of otolith from the Baiyangdian is higher than that r from the Miyun Reservoir.
Comprehensive analysis shows that: the water quality will not affect polymorph of calcium carbonate in otolith basically, but a slight impact on lattice parameters, Mg and the heavy metals Cu and Pb led to aberration of lattice parameters of calcium carbonate. The contents of Cu and Pb is the main factor to the the difference of Micro-CT value of otolith from different waters. The contents of Cu and Pb which have a high atomic number are higher in otolith from the Baiyangdian waters, resulting of the high density voxels. Cu and Pb have the characters: high atomic number, high electronic binding energy ,high density and the atomic structure is tightness .The X-ray collides with Cu and Pb and can be absorbed largely when the X-ray irradiate the otolith, which led to large absorption coefficient and the high value of Micro-CT. To sum up, information on heavy metals with high atomic number in the carp otolith can be reflected by statistical comparison of Micro-CT data. Elements in otoliths have the similar distribution trend with elements of the waters and can be obviously enriched. Therefore, there is the coupling relationship between Micro-CT character of carp otolith and the heavy metals in waters, which can be used to direct the information of the heavy metals in waters as typomorphic character.
引文
[1]段昌群.环境生物学[M].北京:科学出版社,2004: 1～397
[2] Pannella G. Fish otoliths: daily growth layers and periodical patterns[J]. Science, 1971,173:1124～1127
[3] Devereux I. Temperature measurements from oxygen isotope ratios of fish otoliths [J]. Science, 1967,155:1684～1685
[4] GEFFEN A J. Otolith ring deposition in relation to growth rate in the herring (Clupeaharengus) and turbot (Scophthalmus maximus) larvae[J]. Mar Biol (Berl), 1982, 71: 317～326
[5]解玉浩.有明银鱼耳石显微结构和微化学研究[J].动物学报,2001,47(2):215～220
[6] Hanson P J , Zdanowicz V S. Elemental comparison of otoliths from Atlantic croaker along estuarine pollution gradient [J]. Journal of Fish Biology, 1999,54:656～668
[7]杨良锋.北京周边地区鲤鱼耳石矿物与环境响应研究: [博士学位论文].北京:中国地质大学(北京), 2007.1～131
[8]李建国.白洋淀湿地水环境安全评价研究: [硕士学位论文].河北:河北农业大学,2005
[9]李亚鹏.白洋淀的水环境质量与保护对策研究: [硕士学位论文].河北:河北农业大学,2006
[10]张芸,王秀兰,李兵.白洋淀污染机理及防治探讨[J].水资源保护,1999, 58 : 29～32
[11]杨卓,李贵宝,王殿武,等.白洋淀底泥重金属污染现状调查及评价研究[J].河北农业大学学报, 2005, (28)5: 20～26
[12]葛晓立,刘晓端,潘小川等,密云水库水体的地球化学特征[J].岩矿测试,2003, 22(1):44～48
[13]王晓燕,郭芳,蔡新广,胡秋菊,密云水库潮白河流域非点源污染负荷[J].城市环境与城市生态, 2003, 16(1): 3～33
[14]杜桂森,孟繁艳,李学东,等.密云水库水质现状及发展趋势[J].环境科学, 1999,3(20): 110～112
[15]张治国,王卫民.鱼类耳石研究综述[J].湛江海洋大学学报,2001,21(4):78～83
[16]罗军燕.用于湖库水质评价的鲤鱼耳石热释光标型研究: [硕士学位论文].北京:中国地质大学(北京), 2006.1～50
[17]解玉浩.鱼类耳石日轮[J].生物学通报,1995,30(11): 22～23
[18]高永华,冯庆玲,李卓,等.人工控制水化学条件下培养的鲤鱼耳石微观形貌的SEM观察[J].复合材料学报, 2008, 25(6): 118～122
[19]李国武,熊明,施倪承,等. SMART APEX- CCDX射线单晶衍射仪的粉晶衍射新技术及应用[J].地学前缘, 2003,10(2): 492～494
[20] Genant HK , Gordon C,Jiang Y ,et al .Advanced imaging of bone macro and micro structure[J]. Bone, 1999,25: 149～152
[21] Buchman SR , Sherick DG ,Goulet RW, et al. Use of microcomputed tomography scanning as a new technique for the evaluation of membranous bone [J]. J Craniofacial Surg , 1998, 9: 48～54
[22]许宋锋,王臻. Micro-CT在骨科的应用和进展[J].中国骨肿瘤骨病, 2004,3(4): 236～241
[23]朱锋,邱勇,杨晓恩等.青少年特发性和先天性脊柱侧凸患者的骨微结构及骨密度比较.中华骨科杂志, 2005, 5(9): 541～545
[24]赵阳升,孟巧荣,康天合等.显微CT试验技术与花岗岩热破裂特征的细观研究[J].岩石力学与工程学报, 2008, 27(1): 28～34
[25] Amos C L,Sutherland T F,Badzijewski B,et al. A rapid technique to determine bulk density of fine-grained sedments by X-ray computed tomography [J]. Journal of Sedimentary Research ,1996, 66(5): 1023～1024
[26]张笑归,刘树庆,窦铁岭,等.白洋淀水环境污染防治对策[J].中国生态农业学报,2006,14(2): 27～31
[27]梁宝成,孙雪峰.白洋淀水生态系统危机及其预警[J].南水北调与水利科技,2007, 5(4): 57～60
[28]李胜荣,申俊峰,罗军燕,等.鱼耳石的成因矿物学属性:环境标型及其研究新方法[J].矿物学报, 2007, 27: 241～248
[29]曹烨,李胜荣,杨良锋,等.白洋淀和密云水库野生鲤鱼耳石热释光特征研究[J].岩石矿物学杂志, 2006, 25(5): 450～451
[30]高永华,李胜荣,罗军燕,等.热释光计量仪在鱼耳石成因矿物学研究中的应用分析测试[J].现代仪器, 2006, 3: 67～68
[31]杨良锋,李胜荣,王月文,等.不同水域鲤鱼耳石CaCO3晶体结构特征与环境响应初探[J].地球学报, 2007, 28(2): 195～204
[32]杨良锋,李胜荣,罗军燕,等.不同水域鲤鱼耳石微化学特征及其环境指示意义[J].岩石矿物学杂志, 2006, 25 (6) : 511～517
[33] http://www.szsbetter.com/cn/2.html
[2] Pannella G. Fish otoliths: daily growth layers and periodical patterns[J]. Science, 1971,173:1124～1127
[3] Devereux I. Temperature measurements from oxygen isotope ratios of fish otoliths [J]. Science, 1967,155:1684～1685
[4] GEFFEN A J. Otolith ring deposition in relation to growth rate in the herring (Clupeaharengus) and turbot (Scophthalmus maximus) larvae[J]. Mar Biol (Berl), 1982, 71: 317～326
[5]解玉浩.有明银鱼耳石显微结构和微化学研究[J].动物学报,2001,47(2):215～220
[6] Hanson P J , Zdanowicz V S. Elemental comparison of otoliths from Atlantic croaker along estuarine pollution gradient [J]. Journal of Fish Biology, 1999,54:656～668
[7]杨良锋.北京周边地区鲤鱼耳石矿物与环境响应研究: [博士学位论文].北京:中国地质大学(北京), 2007.1～131
[8]李建国.白洋淀湿地水环境安全评价研究: [硕士学位论文].河北:河北农业大学,2005
[9]李亚鹏.白洋淀的水环境质量与保护对策研究: [硕士学位论文].河北:河北农业大学,2006
[10]张芸,王秀兰,李兵.白洋淀污染机理及防治探讨[J].水资源保护,1999, 58 : 29～32
[11]杨卓,李贵宝,王殿武,等.白洋淀底泥重金属污染现状调查及评价研究[J].河北农业大学学报, 2005, (28)5: 20～26
[12]葛晓立,刘晓端,潘小川等,密云水库水体的地球化学特征[J].岩矿测试,2003, 22(1):44～48
[13]王晓燕,郭芳,蔡新广,胡秋菊,密云水库潮白河流域非点源污染负荷[J].城市环境与城市生态, 2003, 16(1): 3～33
[14]杜桂森,孟繁艳,李学东,等.密云水库水质现状及发展趋势[J].环境科学, 1999,3(20): 110～112
[15]张治国,王卫民.鱼类耳石研究综述[J].湛江海洋大学学报,2001,21(4):78～83
[16]罗军燕.用于湖库水质评价的鲤鱼耳石热释光标型研究: [硕士学位论文].北京:中国地质大学(北京), 2006.1～50
[17]解玉浩.鱼类耳石日轮[J].生物学通报,1995,30(11): 22～23
[18]高永华,冯庆玲,李卓,等.人工控制水化学条件下培养的鲤鱼耳石微观形貌的SEM观察[J].复合材料学报, 2008, 25(6): 118～122
[19]李国武,熊明,施倪承,等. SMART APEX- CCDX射线单晶衍射仪的粉晶衍射新技术及应用[J].地学前缘, 2003,10(2): 492～494
[20] Genant HK , Gordon C,Jiang Y ,et al .Advanced imaging of bone macro and micro structure[J]. Bone, 1999,25: 149～152
[21] Buchman SR , Sherick DG ,Goulet RW, et al. Use of microcomputed tomography scanning as a new technique for the evaluation of membranous bone [J]. J Craniofacial Surg , 1998, 9: 48～54
[22]许宋锋,王臻. Micro-CT在骨科的应用和进展[J].中国骨肿瘤骨病, 2004,3(4): 236～241
[23]朱锋,邱勇,杨晓恩等.青少年特发性和先天性脊柱侧凸患者的骨微结构及骨密度比较.中华骨科杂志, 2005, 5(9): 541～545
[24]赵阳升,孟巧荣,康天合等.显微CT试验技术与花岗岩热破裂特征的细观研究[J].岩石力学与工程学报, 2008, 27(1): 28～34
[25] Amos C L,Sutherland T F,Badzijewski B,et al. A rapid technique to determine bulk density of fine-grained sedments by X-ray computed tomography [J]. Journal of Sedimentary Research ,1996, 66(5): 1023～1024
[26]张笑归,刘树庆,窦铁岭,等.白洋淀水环境污染防治对策[J].中国生态农业学报,2006,14(2): 27～31
[27]梁宝成,孙雪峰.白洋淀水生态系统危机及其预警[J].南水北调与水利科技,2007, 5(4): 57～60
[28]李胜荣,申俊峰,罗军燕,等.鱼耳石的成因矿物学属性:环境标型及其研究新方法[J].矿物学报, 2007, 27: 241～248
[29]曹烨,李胜荣,杨良锋,等.白洋淀和密云水库野生鲤鱼耳石热释光特征研究[J].岩石矿物学杂志, 2006, 25(5): 450～451
[30]高永华,李胜荣,罗军燕,等.热释光计量仪在鱼耳石成因矿物学研究中的应用分析测试[J].现代仪器, 2006, 3: 67～68
[31]杨良锋,李胜荣,王月文,等.不同水域鲤鱼耳石CaCO3晶体结构特征与环境响应初探[J].地球学报, 2007, 28(2): 195～204
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